JP2002105174A - Flame-retardant epoxy resin composition and its application - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant epoxy resin composition free from a noxious substance such as a halogen or antimony. SOLUTION: The flame-retardant epoxy resin composition contains (A) at least one kind of epoxy resin and (B) a heterocyclic compound containing phosphorus and nitrogen shown by the general formula (I) (wherein, m is an integer of 0-2; n is an integer of 3-7; and at least one of m is not 2), which is used as a curing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant epoxy resin composition and its use. The flame-retardant epoxy resin composition of the present invention does not contain a commonly used flame-retardant substance such as a halogen compound and antimony trioxide, and has a high level of flame retardancy that meets the flame-retardant standards described in UL94V-0. Flammable, electronic products,
It can be widely used as a material for applications requiring heat resistance and flame retardancy in related fields such as electric products and automobile parts.

[0002]

BACKGROUND ART Generally used epoxy compounds include:
Its own flammability limits its use.
It is known that the addition of a resin having a functional group such as a halogen or a halogenated alkyl group to such an epoxy compound helps to improve the flame retardancy of the epoxy compound. Currently, in order to impart flame retardancy to a polymer or its composition, a resin composition having high heat resistance, which is mainly a halogenated organic compound or an oxide such as antimony or vanadium as a flame retardant substance, is generally used. However, in order to impart the required high flame retardancy, it is necessary to add a very large amount of metal oxides such as the halogenated resin or polymer or antimony,
There's a problem.

[0003] Epoxy resins are widely used in the field of composite materials and many fields because of their simple processing properties, excellent safety, mechanical properties and chemical properties.
There are many applications such as painting, electrical insulation materials, civil engineering materials, adhesives and laminates. In addition, epoxy resin has a strong adhesive strength to reinforcing materials such as glass fiber, does not generate volatile components when cured, and has relatively low molding shrinkage, so it is used for manufacturing laminates. Is also used. Laminates manufactured using these epoxy resins are used in large quantities as materials for electrical and electronic products and their components.

In the production of printed boards, which are of particular importance today, in addition to the precision of the electric circuits on the printed boards, it is required that the laminates also have excellent electrical properties, mechanical properties and processing heat resistance. I have. Usually common
Many such as FR4 laminates and rubber lining copper foil for layering,
Since the glass transition temperature of the cured resin is about 130 ° C,
In the process of manufacturing a printed board, there is ample risk of cracking or breaking the laminated board when performing a cutting step or a drilling step exceeding 200 ° C. and a welding operation at 270 ° C. or more. For this reason, resins having high thermal stability and high glass transition temperature are being researched and developed one after another. Another important property of a printed board laminate is flame retardancy. For example, the flame retardancy of a printed board is absolutely essential for applications such as aircraft, automobiles, and mass transportation.

[0005] In order to impart flame retardancy to a laminated board material, it is necessary to use a substance having flame resistance and capable of lowering flame resistance. Epoxy resin / glass fiber (or organic fiber)
For laminates or insulating materials for layering, the addition of halogen compounds, especially bromine-containing epoxy resins and hardeners, and the use of flame retardant aids such as diantimony trioxide, etc., usually result in severe damage to the laminates. Flame retardant properties (eg, UL94
Requirements such as V-0). However, the above UL94V-0
In order to meet the standard, the bromine content as a flame retardant in an epoxy resin is usually 21% or more, and it is necessary to use antimony trioxide or another flame retardant auxiliary. However, epoxy resins and antimony trioxide having a high bromine content are harmful to human health. On the other hand, these materials produce corrosive free radicals of bromine and toxic gases such as hydrogen bromine during combustion, and aromatic compounds with a high bromine content include brominated furans and brominated dioxins. There are adverse effects on human health and the environment, such as the emission of toxic substances. There is an urgent need for new flame-retardant materials and flame-retarding methods that can solve such problems. In particular, at present, when FR-4 class epoxy resin glass fiber laminates are used in large quantities in electronic and electrical products and their components, flame-retardant epoxy resin materials that do not harm humans and are environmentally friendly Further active research and development is needed.

Recently, many new flame retardant materials have been developed for the purpose of maintaining human health and reducing sources of environmental pollution. As a result, a technique of using a phosphorus compound as a non-halogen flame retardant instead of a bromine compound which has been used so far has been widely accepted.
At present, phosphorus compounds are widely used as environmentally friendly flame retardants in a new era. For example, red phosphorus and organic phosphorus compounds (eg, trifel phosphate, triphenyl methyl phosphate, etc.) are often used as flame retardants in place of conventionally used bromine compounds, and are used for polymer materials and curable resin materials. Although these compounds are useful for improving the flame retardancy, when these compounds are added to the resin, it is necessary to directly add a large amount of the above flame retardant in order to impart flame retardancy. Because of its low molecular weight, it is easy to cause relatively high migration, directly affecting the properties of the resin material, and adversely affecting properties such as electrical properties, adhesive strength, and heat resistance. , There was a problem in use.

Subsequently, a technique has been developed in which a reactive phosphorus-containing epoxy resin is used as a flame-retardant composition instead of a commonly used bromine-containing or brominated epoxy resin. For example, US Pat. No. 5,376,453 discloses a laminate using a composition of a phosphoric acid ester having an epoxy group and a curing agent containing nitrogen. However, if the composition is UL94V-
Since it is difficult to achieve the flammability standard of 0, it is necessary to increase the phosphorus content by adding an epoxy resin containing many phosphate esters. Further, US Pat. No. 5,458,978 discloses a composition formed from an epoxy phosphate, a nitrogen-containing epoxy resin, and a metal composite curing agent. This composition has a glass transition temperature of about 175 ° C., and has a performance close to the flame retardancy of UL94V-0 (42 seconds, critical value is 50 seconds). Further, US Pat. Nos. 4,973,631 and 5,086,156 disclose that a trialkylenephosphine oxide having a substituent having an active hydrogen (for example, an amino group) is used alone or in combination with another amino curing agent. The epoxy resin is cured by doing this, and phosphorus is added to the resin by such a curing method, but because of the low phosphorus content, flame retardancy cannot be expected. Are not described. As seen in the patents disclosed above,
As a technique for increasing the flame retardancy, the result of achieving the flame retardancy standard has been obtained only by constantly adding various or high contents of phosphorus compounds, but using such a large number or a large amount of additives This means that it is always difficult to control the processing conditions of the product and that the quality of the product deteriorates.

[0008]

DISCLOSURE OF THE INVENTION In view of the adverse effects on the environment of conventional flame-retardant substances to which harmful substances including halogen and antimony have been added, the researchers of the present invention have intensively studied to solve these problems. To find an environmentally friendly flame-retardant compound, thereby completing the present invention. That is, an object of the present invention is to provide a heterocyclic compound containing phosphorus and nitrogen which has a functional group capable of reacting with an epoxy group of an epoxy resin and is used as a curing agent component of an epoxy resin composition.

According to the present invention, the flame resistance of the epoxy resin composition can be enhanced by adding an effective amount of a heterocyclic compound containing phosphorus and nitrogen to the epoxy resin. Epoxy resin composition formed from the above phosphorus, nitrogen-containing heterocyclic compound and epoxy resin, in addition to improving the flame retardancy, further shows the effect of enhancing electrical properties, mechanical properties and excellent workability, It is not necessary to add a large amount of a flame retardant, the production cost is low, the glass transition temperature is high, and the heat resistance is excellent. Therefore, the flame retardant epoxy resin composition of the present invention requires the flame retardancy. Prepreg,
It is useful as a laminate, an insulating material for increasing layers, and a material for a printed board.

More specifically, the present invention relates to a flame-retardant epoxy resin composition, which comprises, as features, the following compounds: (A) at least one epoxy resin; (B) the following used as a curing agent for the epoxy resin: Heterocyclic compounds containing phosphorus and nitrogen represented by the general formula (I):

[0011]

Embedded image

In the formula, m represents an integer of 0 to 2, and n represents 3 to 7
Indicates an integer. However, at least one of m does not represent 2. The flame-retardant epoxy resin composition comprising the above components (A) and (B) exhibits excellent flame retardancy, and is required for components such as composite materials, laminates, printed boards and electronic and electric products. It is possible to selectively add a phosphorus-free curing agent, a curing accelerator, a solvent, and other additives depending on the application.

In the present invention, the epoxy resin as the component (A) of the composition may be a general epoxy compound, and includes an epoxy resin composed of one or more kinds of epoxy compounds. These epoxy resins preferably have an epoxy equivalent weight (EEW) of 600 or less. As the epoxy resin used in the present invention, for example, bisphenol, phenol,
Benzenediphenol, bisdiphenol, naphthalene, alkyl group, olefin group, cyclic hydrocarbon, nitrogen-containing heterocycle, cresol-aldehyde, phenolic resin,
An epoxy compound having an epoxy group modified by a functional group such as siloxane or polysiloxane and an aromatic phosphate ester, and the like can be given. The flame-retardant epoxy resin composition of the present invention contains epoxy resin components having the following epoxy groups: glycidyl ether, glycidylamine, glycidyl thioether and glycidyl carboxylate. Among them, glycidyl ether modified with bisphenol, bisdiphenol, benzenediphenol, polyol and silicone is more preferable.

In the present invention, specific examples of the glycidyl ether modified with the above specific functional group include, for example, a —Ph—X—Ph— group (where X is CH ₂ , C (CH ₃ ) ₂ , CH (C
_{H 3), O, S,} C = O, indicating, for example, SO ₂₎ modified diglycidyl ether are exemplified by bisphenol having, in its specific examples, bisphenol A glycidyl ether, bisphenol F glycidyl ether, bisphenol AD glycidyl ether, bisphenol S glycidyl ether, tetramethyl bisphenol A glycidyl ether, tetramethyl bisphenol F glycidyl ether, tetramethyl bisphenol AD glycidyl ether, tetramethyl bisphenol S glycidyl ether, and the like.

Specific examples of the glycidyl ether modified with bisdiphenol include, for example, 4,4′-diphenol glycidyl ether, 3,3′-dimethyl-4,4′-diphenol glycidyl ether, 3 ', 5,5'-tetramethyl
-4,4'-diphenol glycidyl ether and the like. Specific examples of benzenediphenol glycidyl ether include, for example, resorcing glycidyl ether, hydroquinone glycidyl ether, and isobutylhydroquinone glycidyl ether.

Specific examples of the phenol / aldehyde polyglycidyl ether include, for example, phenol / aldehyde polyglycidyl ether, cresol phenol aldehyde polyglycidyl ether, and bisphenol A phenol aldehyde polyglycidyl ether. Specific examples of the polyglycidyl ether modified with a polyhydroxyl group include, for example, tris (4-
Hydroxyphenyl) methane polyglycidyl ether,
Tris (4-hydroxyphenyl) ethane polyglycidyl ether, tris (4-hydroxyphenyl) propane polyglycidyl ether, tris (4-hydroxyphenyl) butane polyglycidyl ether, tris (3-methyl
4-hydroxyphenyl) methane polyglycidyl ether, tris (3,5-dimethyl-4-hydroxyphenyl) methane polyglycidyl ether, tetrakis (4-hydroxyphenyl) ethane polyglycidyl ether, tetrakis (3,5-dimethyl-4) -Hydroxyphenyl) ethane polyglycidyl ether;

The above-mentioned epoxy resins may be used by mixing one kind or various kinds of epoxy resins. In the present invention, as the epoxy resin component, one having two functional groups such as bisphenol A polyglycidyl ether and resolving ricidyl ether and three functional groups such as tris (4-hydroxyphenyl) methane polyglycidyl ether are used. And those having four functional groups, such as tetrakis (4-hydroxyphenyl) ethane polyglycidyl ether, or cresol phenol polyglycidyl ether are preferable. Used in mixed form.

The epoxy resin component used in the present invention may be modified with a silicone or a rubber copolymer. As the above-mentioned silicone compounds,
For example, a siloxane having an amino group at a terminal (for example,
Nihon Shin-Etsu company product name SF-8012 etc.)
As the rubber copolymer, for example, a copolymer having a carboxyl group at the terminal of butadiene and acrylonitrile (for example, CTBN product name of Goodrich Company of America)
And a copolymer having an amino group at the terminal of butadiene and acrylonitrile (eg, ATBN, a product name of a product of Goodrich Company in the United States).

In the flame-retardant epoxy resin composition of the present invention, in order to enhance the flame retardancy and heat resistance, a heterocyclic compound containing phosphorus and nitrogen as the component (B) is used. It has a functional group that reacts with an epoxy group and is used as an epoxy resin curing agent, and its structure is represented by the following formula (I)
Indicated by

[0020]

Embedded image

In the formula, m represents an integer of 0 to 2, and n represents an integer of 3 to 7. However, at least one of m does not show 2. In the flame-retardant epoxy resin composition of the present invention, (A)
The usage rate of the epoxy resin of the component and the heterocyclic compound containing phosphorus and nitrogen of the component (B) is based on the epoxy equivalent of the epoxy resin (A) and the curing of the heterocyclic compound containing a phosphorus and nitrogen having a functional group capable of reacting with the epoxy group. Determined by the equivalent of the active hydrogen of the agent (B), this is 100% based on the epoxy equivalent.
In this case, the reaction active hydrogen of the curing agent (B) is usually used in an amount of 20 to 95% equivalent, and the reaction active hydrogen equivalent of the curing agent (B) is preferably used in an amount of 40 to 90%, particularly preferably 50 to 90%. Most preferably, ~ 90% is used.

On the other hand, the flame-retardant epoxy resin composition of the present invention further contains phosphorous in order to be used in various high heat-resistant material fields, such as laminates, IC sealing materials, and high heat-resistant powder coating. , A curing accelerator (D), a curing accelerator (D), a solvent (E), and other additives (F) that do not contain any. Further, the viscosity is adjusted by adding a solvent to prepare a varnish, and the varnish is used for producing a film having a flame retardant effect, a laminated board, an insulating material for increasing layers, and the like.

Examples of the phosphorus-free curing agent include bisphenol, benzenediol, phenol,
Naphthalene, alkylene hydrocarbon, cyclic hydrocarbon, nitrogen heterocyclic compound, phenolic resin, siloxane, polysiloxane, Ph-X-Ph- group (where X is CH ₂ , C (CH ₃ ) ₂ , CH
(CH ₃ ), O, S, C = O, SO ₂ etc.), polyamines, polythiols and polycarbonates. Examples of the phosphorus-free curing agent include amines, polyhydroxy Examples include phenol and phenol / aldehyde. Specific examples of the amines include:
For example, dicyanodiamide (NH ₂ C (NH) (NHCN)), diaminodiphenylmethane (DDM) and the like can be mentioned. Examples of the polyhydroxyphenol include tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane, tris (4-hydroxyphenyl) propane, tris (4-hydroxyphenyl) butane, and tris (3-methyl- 4-hydroxyphenyl) methane, tris (3,5-dimethyl-4-hydroxyphenyl) methane, tetrakis (4-hydroxyphenyl) ethane, tetrakis (3,5-dimethyl-4-hydroxyphenyl) ethane and the like. Specific examples of the phenol / aldehyde include, for example, a phenol / formaldehyde condensate, a cresol / phenol aldehyde condensate, and a bisphenol A phenol aldehyde condensate.

As the above-mentioned curing agent not containing phosphorus, a commonly used curing agent is, for example, dicyanodiamide (NH ₂ C (NH)).
(NHCN)), diaminodiphenylmethane (DDM), diethyltriamine (DETA), diaminodibenzenesulfone (DDS), metaphenyldiamine (MPDA), methyldianiline (MDA), maleic acid (MA), phthalic anhydride ( P
A), hexahydrophthalic anhydride (HHPA), tetrahydrophthalic anhydride (THPA) and the like.

The content of the phosphorus-free curing agent is determined by the reaction active hydrogen equivalent and the epoxy equivalent of the epoxy resin. The reaction active hydrogen of the phosphorus-free curing agent is defined assuming that the epoxy equivalent of the epoxy resin is 100%. The equivalent is usually 20 ~
It is 95%, preferably 40-90%, especially 50-90%. In the flame-retardant epoxy resin composition of the present invention, a curing accelerator can be added as required. As such a curing accelerator, for example, a tertiary amine, a tertiary phosphine, a quaternary ammonium salt, a quaternary phosphonium salt and an imidazole compound or a mixture thereof is used.
Specific examples of the tertiary amine include, for example, triethylamine, tributylamine, dimethylaminoethanol, tris (N, N-dimethylaminomethyl) phenol, N, N-
Specific examples of tertiary phosphines include, for example, triphenylphosphine; specific examples of quaternary ammonium salts include, for example, tetramethylammonium chloride, tetramethylammonium bromide, tetramethyl Ammonium iodide, triethylphenylmethylammonium chloride, triethylphenylmethylammonium bromide, triethylphenylmethylammonium iodide and the like; specific examples of the quaternary phosphonium salt include, for example, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide,
Tetrabutylphosphonium iodide, tetrabutylphosphonium lipinate acetate complex, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide, Ethyl triphenyl phosphonium lipinate acetate complex, ethyl triphenyl phosphonium lipinate phosphate complex, propyl triphenyl phosphonium chloride, propyl triphenyl phosphonium bromide, propyl triphenyl phosphonium iodide, butyl triphenyl phosphonium chloride, butyl triphenyl phosphonium Bromide, butyltriphenylphosphonium Etc. can be mentioned are iodides; imidazole compounds such as 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-dodecyl over imidazole, etc. descriptor decyl imidazole to 2-. More preferred curing accelerators include quaternary phosphonium salts and imidazole compounds, even more preferably 2-methylimidazole, 2-phenylimidazole, ethyltriphenylphonium lipinate acetate complex, butyltriphenylphonium bromide Is mentioned. The curing accelerators can be used alone or as a mixture.

In the flame-retardant epoxy resin composition of the present invention, the content of a curing accelerator optionally used is 0.005 to 5.0% by weight based on the total weight of the composition, and more preferably. , 0.05-4.5% by weight, more preferably 0.1
~ 4.0 wt%, most preferably 0.15-3.0 wt%. In the composition of the present invention, when the content of the added curing accelerator exceeds 5.0% by weight, the reaction time can be shortened, but a reaction by-product is generated or the conversion rate of the curing reaction is uniform. May have a bad effect. Conversely, if the content of the curing accelerator is less than 0.005% by weight, the reaction rate may be low and the effect may be poor.

A varnish can be prepared by adding a solvent to the flame-retardant epoxy resin composition of the present invention. By adding a solvent to the epoxy resin composition of the present invention, its viscosity is reduced to 20.
Adjusted to ~ 500 cps / 25 ° C, used to manufacture films in impregnated and dry form, or as an insulating layer
Used for painting of the ectric layer build-up process).

As a solvent applied to the preparation of the above varnish,
For example, organic benzenes, ketones, aprotic solvents, ethers and esters, and the like are used. Examples of organic benzenes include, for example, toluene and dimethylbenzene, and examples of ketones include, for example, acetone,
Methyl ethyl ketone, methyl isobutyl ketone, etc .; aprotic solvents include, for example, N, N-dimethylformamide and N, N-getylformamide; ethers include, for example, ethylene glycol monomethyl ether, propylene Glycol monomethyl ether; esters include, for example, ethyl acetate, ethyl isopropionate and the like.

In the present invention, when an epoxy resin composition is prepared into a varnish in the present invention, a curing accelerator may be added,
Selectively add a solvent to increase its viscosity from 20 to 500 cps / 25 ° C
And the gelation time is 30-500 seconds / 1
It can be controlled in the range of 71 ° C. further,
For the purpose of use and special applications, additives and modifiers which are generally commercially available may be added to the flame-retardant epoxy resin composition of the present invention. Thus, examples of the additive include a heat stabilizer, a light stabilizer, an ultraviolet absorber, a plasticizer, and an inorganic filler. It is to be noted that a halogen-based compound or diantimony trioxide can be used as an additive or a modifier. However, from the viewpoint of environmental conservation and safety, the composition of the present invention uses such an additive or modifier. Care is taken not to use bulking agents.

After the flame-retardant epoxy resin composition disclosed in the present invention is prepared into a varnish, a copper foil,
A laminate of a flame-retardant epoxy resin composition of a fibrous support and a compound containing phosphorus and nitrogen is produced. The flame-retardant epoxy resin composition of the present invention is, for example, an organic or inorganic material (eg, glass, metal, carbon fiber, inorganic fiber (eg, boron fiber), cellophane, artificial fiber, organic polymer material, etc.). And other fiber materials. As an example, a varnish prepared with the epoxy resin composition of the present invention is impregnated with glass fiber fabric, and the impregnated glass fiber fabric is heated and dried to obtain a film.
Such a film does not change its properties even when stored at room temperature for several months, and has excellent storage stability. Further, the film is used for the production of a composite laminate or used alone for other film adhesive layers. Furthermore, using one or many combinations, place copper foil on one side of the film, or on both the upper and lower sides, and heat the above film or the combined object under pressure to obtain size stability, chemical resistance, and corrosion resistance. ,
A laminate composite material having significantly improved hygroscopicity and electrical properties and having extremely excellent properties as compared with conventional products can be obtained. Such a composite material is applied to the manufacture of products and parts used in fields such as electronics, electricity, space science, and transportation.

Specifically, it is used for, for example, a printed board and a multilayer circuit board; or a rubber-backed copper foil for increasing a layer on a copper foil by precision painting (for example, a resin-coated copper foil (Resin coated copper foil)). foil)); applied to a release film to produce an insulating film for thickening; or impregnated with glass fiber fabric using a varnish prepared from a phosphorus-containing epoxy resin composition. It is also used to produce a backing-coated copper foil for layering by coating or drying the epoxy resin composition on a varnished copper foil.

The backing rubber-coated copper foil for such a layer is excellent in storage stability and can be stored at room temperature for several months. Further, a thin and high-density printed board can be manufactured by using the hot pressing process. The method for curing the flame-retardant epoxy resin composition containing phosphorus of the present invention is usually 20
Cure the composition at a reaction temperature of ~ 350 ° C, but with a 50 ~ 3
It is preferable to cure at a temperature of 00 ° C.
It is more preferable to cure at a temperature of 50 ° C, especially 120 to 2
Most preferably, it is cured at a temperature of 20 ° C.

It is necessary to carefully control the above curing reaction temperature. If the reaction temperature exceeds 350 ° C., side reactions are likely to occur, and it is difficult to control the reaction rate. Further, there is a possibility that the deterioration speed of the resin may be increased. When the reaction temperature is lower than 20 ° C., the efficiency becomes poor, and the characteristics of the resulting resin are difficult to withstand the demand for use at high temperatures.

The flame-retardant epoxy resin composition containing phosphorus of the present invention can be prepared without adding other processing aids and flame-retardant additives.
At the same time, the flame retardancy and heat resistance of the epoxy resin can be improved. The present invention provides a phosphorus-containing nitrogen-containing heterocyclic compound having a functional group that reacts with an epoxy group,
The phosphorus-containing, nitrogen-heterocyclic compound epoxy resin composition of the present invention and the other phosphorus-containing, nitrogen compound epoxy resin composition impart high flame retardancy and thermal stability, and have the effect of improving mechanical properties. .

[0035]

The present invention will be described in more detail with reference to the following synthesis examples and examples, but the present invention is not limited to these examples. Epoxy equivalent (EE
W, Epoxy Equivalent Weight, varnish viscosity (Viscosit
y), solid content, etc. were measured according to the following methods. (1) Epoxy equivalent (EEW): An epoxy resin was dissolved in a chlorobenzene: chloroform = 1: 1 solvent, and HBr /
Titration was performed using glacial acetic acid, and the epoxy equivalent was measured by a method according to ASTM D1652. Note that crystal violet was used as an indicator. (2) Viscosity: The phosphorous-containing epoxy resin varnish was left in a thermostat at 25 ° C. for 4 hours, and was subjected to a Brookfield viscometer (Brookfield viscometer).
The viscosity was determined at 25 ° C. using a viscosimeter). (3) Solids content: 1 g of a varnish sample of the phosphorus-containing, nitrogen compound epoxy resin composition of the present invention was dried at a temperature of 150 ° C. for 60 minutes, and the weight% of the nonvolatile components was measured.
Obtain the solids content.

The components used in the synthesis examples and examples are described in detail below. Epoxy resin 1: Epoxy resin manufactured by Changchun artificial resin company, trade name is BE188EL, diglycidyl ether of bisphenol A, epoxy equivalent is 185-195g / equivalent. Hydrolytic chlorine content is less than 200ppm, viscosity is 11000-15000cps
/ 25 ° C. Epoxy resin 2: Epoxy resin of Changchun artificial resin company product, trade name is CNE200A80, polyglycidyl ether of cresol-aldehyde condensate, epoxy equivalent is 20
0-220 g / equivalent, using acetone as solvent, solid content is
79.0 to 81.0% by weight.

Epoxy resin 3: Epoxy resin manufactured by Changchun artificial resin company, trade name is BEB530A80, diglycidyl ether of tetrabromobisphenol A, epoxy equivalent is 430 to 450 g / equivalent, and bromine content is 18.5 to 20.5% by weight. Epoxy resin 4: Epoxy resin manufactured by Changchun artificial resin company, trade name is BEB526A80, diglycidyl ether of tetrabromobisphenol A, epoxy equivalent is 410
430 g / equivalent, bromine content 19.0-21.0% by weight.

Curing agent A: 10% solution in dicyanodiamide, dimethylformamide (DMF). Curing accelerator: 2-methylimidazole, 10% solution in DMF solvent. [Synthesis Example]: Synthesis of a heterocyclic compound containing phosphorus and nitrogen. A 1 L high-pressure glass reactor equipped with a temperature indicator and a cooling reflux device was used, and connected to a hydrochloric acid absorption tank through a glass tube at the end of the reflux device. 300 ml of chlorobenzene, 150 ml of phosphorus trichloride and 0.5 g of magnesium chloride were added to the reactor, while 500 ml of a 50% by weight aqueous sodium hydroxide solution was placed in a hydrochloric acid absorption tank, and the reactor was heated. 131
Chlorobenzene starts refluxing at 20 ° C., at which time 20 ml /
After stirring reaction was continued for 1 hour through chlorine gas at a rate of min, the introduction of chlorine gas was stopped, and ammonia gas was introduced at a rate of 20 ml / min instead. At this time, it was observed that the hydrochloric acid gas gradually entered the hydrochloric acid absorption tank through the glass tube.
After the stirring reaction was continued for 3 hours, the control valve in the reflux path was closed, and simultaneously the control valve in the distillation path was opened to remove chlorobenzene by distillation for 30 minutes. 4-dioxane 300m
l, 450 g of phenol and 0.5 g of tetra-n-butylammonium chloride were added, the control valve in the distillation path was closed, and the control valve in the reflux path was opened.
Heating to 1 ° C. started refluxing the 1,4-dioxane solution. After the reaction was continued for 2 hours, the control valve in the reflux path was closed, ammonia gas was added at 4 kg / cm ² , and the reaction was stirred for 1 hour under pressure. After that, the distillation path was opened to remove unreacted ammonia gas from the system. And at the same time the temperature is 101 ° C
Then, 1,4-dioxane was removed by distillation. Finally, a mixed product of a phosphorus and nitrogen-containing heterocyclic compound having a structure represented by the following general formula (I) was obtained.

[0039]

Embedded image

As a result of analysis by P ³¹ NMR, the reaction product was found to comprise 57.1% of the compound of the general formula (I) represented by n = 3.
Those with n = 4 account for 21.6%, those with n = 5 occupy 1.9%, those with n = 6 occupy 13.9%, and those with n> 7 occupy 5.5%.
Take 200 g of epoxy resin 1 (EEW = 188), mix 200 g of the above-obtained cyclic compound and 2 g of triphenylphosphine, heat to 180 ° C. with stirring, continue the reaction for 2 hours, and until the temperature reaches room temperature. Reduce temperature, epoxy equivalent (EEW)
Of 1228 were obtained. When estimated from the epoxy equivalent value of this reaction product, the amine equivalent of the phosphorus- and nitrogen-containing heterocyclic compound obtained above was 271.

[0041]

Example 1 In a vessel equipped with a stirrer and a cooling condenser, at room temperature, 150.0 g of the epoxy resin 1 and the cyclic phosphine nitrile compound produced by the above synthesis example (the compound represented by the above general formula (I)) ) 216.2g mixed and added 1.23g
A 10% DMF solution (curing accelerator) consisting of 2-methylimidazole and 370 g of methyl ethyl ketone (MEK) are added and mixed by stirring to prepare a varnish of an epoxy resin composition of a heterocyclic compound containing phosphorus and nitrogen. did. The solids content was controlled at about 40-50% by weight and the viscosity was controlled at about 500 cps / 25 ° C.

The glass fiber fabric is impregnated with the epoxy resin varnish of the heterocyclic compound containing phosphorus and nitrogen prepared as described above and dried at 150 ° C. to form a film.
Heating at 120 ° C. for 120 minutes gave a film. Using the above film as a differential scanning calorimeter (DSC, Differential Scan Calorimete)
r, TA2910 type). In addition, a flame test was performed based on the UL-94 flammability test method of the American Electrical Laboratory to evaluate its flame retardancy. The results are shown in Table 1.

[0043]

Example 2 In a vessel equipped with a stirrer and a cooling condenser, at room temperature, 150.0 g of the epoxy resin 1 and the phosphorus- and nitrogen-containing heterocyclic compound prepared by the above synthesis example (the above-mentioned general formula (I)). 132.8 g were mixed, and a 10% DMF solution (hardener accelerator) consisting of 12.6 g of phosphorus-free curing agent A and 0.89 g of 2-methylimidazole and 370 g of methyl ethyl ketone (MEK) were added. By stirring and mixing, an epoxy resin composition varnish of a heterocyclic compound containing phosphorus and nitrogen was obtained.

According to the test method used in Example 1, the glass transition temperature and flame retardancy of the epoxy resin composition varnish of the above prepared heterocyclic compound containing phosphorus and nitrogen were measured. The results are shown in Table 1.

[0045]

Example 3 In a vessel equipped with a stirrer and a cooling condenser, at room temperature, 150.0 g of the epoxy resin 2 and the heterocyclic compound containing phosphorus and nitrogen prepared in the above Synthesis Example (the above-mentioned general formula (I)). (Shown) 184.8 g, 10% DMF solution (hardening accelerator) consisting of 1.30 g of 2-methylimidazole and 370 g of methyl ethyl ketone (MEK) were added, and mixed by stirring.
An epoxy resin composition varnish of a heterocyclic compound containing phosphorus and nitrogen was prepared.

According to the test method used in Example 1, the glass transition temperature and flame retardancy of the epoxy resin composition varnish of the above prepared heterocyclic compound containing phosphorus and nitrogen were measured. The results are shown in Table 1.

[0047]

Example 4 In a vessel equipped with a stirrer and a condenser, 150.0 g of the epoxy resin 2 was added at room temperature to the phosphorus- and nitrogen-containing heterocyclic compound (the above-mentioned general formula (I)). 130.6 g), 10% DMF solution (curing accelerator) consisting of 30.8 g of a phosphorus-free curing agent A, 2.1 g of 2-methylimidazole and 370 g of methyl ethyl ketone (MEK) were added. The mixture was stirred and mixed to prepare an epoxy resin composition varnish of a heterocyclic compound containing phosphorus and nitrogen.

In accordance with the test method used in Example 1, the glass transition temperature and flame retardancy of the epoxy resin composition varnish of the above prepared heterocyclic compound containing phosphorus and nitrogen were measured. Table 1 shows the results.

[0049]

Comparative Example 1 In a vessel equipped with a stirrer and a cooling condenser, 125.0 g of the epoxy resin 3 and 250 g of a phosphorus-free curing agent A were mixed at room temperature, and 0.625 g of 2-methylimidazole was further added. % DMF solution (curing accelerator) and 370 g of methyl ethyl ketone (MEK) were added and mixed with stirring to prepare an epoxy resin composition varnish.

According to the test method used in Example 1, the glass transition temperature and flame retardancy of the epoxy resin varnish prepared above were measured and evaluated. The results are shown in Table 1.

[0051]

Comparative Example 2 In a vessel equipped with a stirrer and a condenser, 125.0 g of epoxy resin 4 and 260 g of a phosphorus-free curing agent A were mixed at room temperature, and 0.625 g of 2-methylimidazole was added. % DMF solution (curing accelerator) and 370 g of methyl ethyl ketone (MEK) were added and mixed by stirring to prepare an epoxy resin composition varnish.

The glass transition temperature and flame retardancy of the epoxy resin varnish prepared above were measured and evaluated according to the same test method used in Example 1 above. The results are shown in Table 1.

[0053]

[Table 1]

[0054]

Examples 5 and 6 and Comparative Examples 3 and 4 Film A (Example 1), Film C (Example 3), Film E (Comparative Example)
1) and a film F (Comparative Example 2) were laminated using eight test sheets, and one 35 μm copper foil was placed on each of the upper and lower sides, and a temperature of 185 ° C. and 25 kg / cm ² was applied. The laminate and the copper foil were pressed under pressure to form a glass fiber fabric layered composite, and the physical properties of these composites (layered composites A, C, E, and F) were measured. Table 2 shows the analysis results in detail.

[0055]

Examples 7 and 8 and Comparative Examples 5 and 6 Examples 1 and 3 and Comparative Example 1
The epoxy resin composition varnish prepared by the method of (2), using 170 g of methyl ethyl ketone as a solvent, the solid content of the varnish is about 70 to 80% by weight, and the viscosity is about 2000 cps / 25 ° C.
A varnish prepared so as to be controlled to a thickness of about 80 μm is coated on the inside of a copper foil of 18 μm and dried at 175 ° C. for 3 minutes. Then, the above sheets (films A, C, and E)
F) and a pressure of 25 kg / cm ² at a temperature of about 180 ° C. for 2 hours to obtain layered plates (A, C, E and F). Further, its heat resistance, electric properties, adhesive strength, and the like were measured. The results are shown in Table 3.

[0056]

[Table 2]

[0057]

[Table 3]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C09K 21/12 C09K 21/12 21/14 21/14 F term (Reference) 4F071 AA42 AC15 AE02 AE03 BC01 4H028 AA38 AA48 BA06 4J002 CD001 CD041 CD051 CD201 EW156 FD019 FD029 FD048 FD058 FD067 FD146 FD157 4J036 AA01 AC01 AC05 AD01 AD08 DA04 DC05 DC41 DC48 DD07 GA02 JA08

Claims (32)

[Claims] (A) at least one type of epoxy resin; (B) an epoxy resin curing agent comprising a heterocyclic compound containing phosphorus and nitrogen represented by the following general formula (I): (Wherein, m represents an integer of 0 to 2 and n represents an integer of 3 to 7, provided that at least one of m does not represent 2). Resin composition. (A) at least one type of epoxy resin; (B) an epoxy resin curing agent comprising a heterocyclic compound containing phosphorus and nitrogen represented by the following general formula (I): (Wherein, m represents an integer of 0 to 2, n represents an integer of 3 to 7, provided that at least one of m does not represent 2.) (C) a phosphorus-free curing agent; A flame-retardant epoxy resin composition containing any one of the following (D) to (F); (D) a curing accelerator; (E) a solvent; and (F) other additives. 3. An epoxy equivalent (EEW) of the epoxy resin (A).
3. The flame-retardant epoxy resin composition according to claim 1, wherein is less than or equal to 600. 4. An epoxy resin (A) comprising bisphenol,
Modified by functional groups such as phenol, benzenediphenol, bisdiphenol, naphthalene, alkyl group, olefin group, cyclic hydrocarbon, nitrogen-containing heterocycle, cresol-aldehyde, siloxane or polysiloxane and aromatic phosphate ester 3. The flame-retardant epoxy resin composition according to claim 1, which is a compound having a modified epoxy group. 5. The flame-retardant epoxy resin composition according to claim 4, wherein the compound having an epoxy group is glycidyl ether, glycidylamine, glycidyl thioether or glycidyl carboxylate. 6. An epoxy resin (A) comprising bisphenol,
3. The flame-retardant epoxy resin composition according to claim 1, which is a glycidyl ether modified with bisdiphenol, benzenediphenol, polyol or silicone. 7. The flame-retardant epoxy resin composition according to claim 6, wherein the modified glycidyl ether is any of the following: a diphenol modified with a bisphenol having a -Ph-Z-Ph- group. Glycidyl ether (where Z is CH ₂ , C (CH ₃ )
₂ , CH (CH ₃ ), O, S, C = O, SO ₂ ); 4,4′-diphenol glycidyl ether, 3,3′-dimethyl-4,4′-diphenol glycidyl ether and 3 Glycidyl ethers modified with bisdiphenol selected from 2,3 ', 5,5'-tetramethyl-4,4'-diphenol glycidyl ether; selected from resorcing ricidyl ether, hydroquinone glycidyl ether and isobutylhydroquinone glycidyl ether Benzene diphenol glycidyl ether; phenol-aldehyde polyglycidyl ether, cresol phenol-aldehyde polyglycidyl ether, and bisphenol A phenol-
Phenol-aldehyde polyglycidyl ether selected from aldehyde polyglycidyl ether; tris (4-hydroxyphenyl) methane polyglycidyl ether, tris (4-hydroxyphenyl) ethane polyglycidyl ether, tris (4-hydroxyphenyl) propane polyglycidyl ether , Tris (4-hydroxyphenyl) butane polyglycidyl ether, tris (3-methyl-4-hydroxyphenyl) methane polyglycidyl ether, tris (3,5-dimethyl-4-hydroxyphenyl)
Polyhydroxyphenylphenol polyglycidyl ether selected from methane polyglycidyl ether, tetrakis (4-hydroxyphenyl) ethane polyglycidyl ether and tetrakis (3,5-dimethyl-4-hydroxyphenyl) ethane polyglycidyl ether; or a mixture thereof . 8. The epoxy resin (A) is bisphenol A
8. The polyglycidyl ether, resorcing ricidyl ether, tris (4-hydroxyphenyl) methane polyglycidyl ether, tetrakis (4-hydroxyphenyl) ethane polyglycidyl ether, cresolphenol-aldehyde polyglycidylether, or a mixture thereof. Flame-retardant epoxy resin composition. 9. The epoxy resin (A) is modified by a silicone compound or a rubber copolymer.
Or the flame-retardant epoxy resin composition according to 2. 10. The flame retardant according to claim 9, wherein the silicone compound is a siloxane having an amino group at the terminal, and the rubber copolymer is a copolymer of butadiene and acrylonitrile having a terminal carboxy group or an amino group. Epoxy resin composition. 11. The contents of the epoxy resin (A) and the heterocyclic compound (B) containing phosphorus and nitrogen are determined by the reaction active hydrogen equivalent and the epoxy group equivalent of the epoxy resin, and the epoxy equivalent is set to 100%. When the reactive hydrogen equivalent of the curing agent is 2
3. The flame-retardant epoxy resin composition according to claim 1, which is 0 to 95%. 12. When the content of the epoxy resin (A) and the heterocyclic compound (B) containing phosphorus and nitrogen is 100% with epoxy equivalent, the reactive hydrogen equivalent of the curing agent is 40 to 90%. 12. The flame-retardant epoxy resin composition according to claim 11. 13. When the content of the epoxy resin (A) and the heterocyclic compound (B) containing phosphorus and nitrogen is 100% of epoxy equivalent, the reactive hydrogen equivalent of the curing agent is 50 to 90%. 13. The flame-retardant epoxy resin composition according to claim 12. 14. The curing agent (C) containing no phosphorus is dicyanodiamide, diaminodiphenylmethane, diethyltriamine, diaminodibenzenesulfone, metaphenyldiamine, methyldianiline, maleic acid, phthalic anhydride, hexahydrophthalic acid. 3. The flame-retardant epoxy resin composition according to claim 2, which is an anhydride or tetrahydrophthalic anhydride. 15. The flame retardant according to claim 2, wherein the phosphorus-free curing agent (C) is a tertiary amine, a quaternary ammonium salt, a tertiary phosphine, a quaternary phosphonium salt or an imidazole compound. Epoxy resin composition. 16. The content of the phosphorus-free curing agent (C) is as follows:
3. The flame-retardant epoxy resin composition according to claim 2, wherein the reaction-active hydrogen equivalent is determined from the reaction-active hydrogen equivalent and the epoxy equivalent of the epoxy resin, and when the epoxy equivalent is 100%, the reaction-active hydrogen equivalent is 20 to 95%. 17. The content of the phosphorus-free curing agent (C) is as follows:
When the epoxy equivalent is 100%, the reactive hydrogen equivalent is 40%.
17. The flame-retardant epoxy resin composition according to claim 16, which has a content of about 90%. 18. The content of the phosphorus-free curing agent (C) is as follows:
When the epoxy equivalent is 100%, the reaction active hydrogen equivalent is 50%.
The flame-retardant epoxy resin composition according to claim 17, wherein the content is from 90% to 90%. 19. The flame-retardant epoxy resin composition according to claim 2, wherein the content of the curing accelerator (D) is 0.005 to 5.0% by weight based on the total weight of the composition. 20. The flame-retardant epoxy resin composition according to claim 19, wherein the content of the curing accelerator (D) is 0.05 to 4.5% by weight based on the total weight of the composition. 21. The flame-retardant epoxy resin composition according to claim 20, wherein the content of the curing accelerator (D) is 0.1 to 4.0% by weight based on the total weight of the composition. 22. The flame-retardant epoxy resin composition according to claim 21, wherein the content of the curing accelerator (D) is 0.15 to 3.0% by weight based on the total weight of the composition. 23. The flame-retardant epoxy resin composition according to claim 2, wherein the solvent (E) is an organic benzene, a ketone, an aprotic solvent, an ether or an ester. 24. The flame-retardant epoxy resin composition according to claim 2, wherein a heat stabilizer, a light stabilizer, an ultraviolet absorber, a plasticizer, or an inorganic filler is used as the other additive (F). 25. A film made from a reinforced material and the flame-retardant epoxy resin composition according to claim 1 or 2. 26. A flame-retardant and high heat-resistant laminate or laminate formed by laminating the film according to claim 25. 27. An insulating material for a layer obtained by applying the flame-retardant epoxy resin composition according to claim 1 to a substrate. 28. A printed board laminate material obtained by hot-pressing a film prepared from the flame-retardant epoxy resin composition according to claim 1 or 2 and a copper foil. 29. The reinforcing material is a fibrous material.
The film according to 1. 30. The reinforcing material is a fibrous material.
The laminate or laminate having flame retardancy and high heat resistance described in 1 above. 31. The base material is a copper foil or a release film.
28. The insulating material for a layer according to 27. 32. A curable composition obtained by curing the flame-retardant epoxy resin according to claim 1 or 2.